Textile finishing material



Patented F ch. 6, 1945 TEXTILE FDNISHING MATERIAL Alfred L. Rummelsburg', Wilmington, DeL, assignor to-Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application February 14, 1942,

Serial No. 430,883

4 Claims.

This invention relates to an improved finishing composition for textile fabrics, to an improved textile fabric, and to methods of production thereof. More particularly, it relates to a. finishing composition having as a binding agent a polymerized terpene resin.

Heretofore; textile fabrics have been treated with finishing compositions having a binding agent (stiffening agent or agglutinate) casein,

gelatin, glue or gums, as, for example, traga- -canth, tragasol, or mucilage, or, as more commonly used, starch in combination with suitable fillers, softeners, and/or deliquescents, with the object of improving the appearance and handle of the fabric. A common finishing treatment consists of back-filling a fabric with a composition comprising as a filler, china clay or talc; as a softener, oils, fats, waxes, soap, or sulfonated oils; and as a binding agent} starch. This treatment is generally applied to one side of the fabric, thereby closely filling in the open weave of the fabric to increase the weight and improve the handle of the material. This type of mixture is not entirely satisfactory for backfilling inasmuch as the starch does not satisfactorily bind the talc or china clay to the fabric, and on handling, the starch-back-filling composition dusts out, thereby altering the body, weight, and handle as well as the appearance of the fabric. Further, in starch-backfilling compositions, particularly where a colored fabric is being treated, the starch composition, which has a relatively high solids content, has a tendency to cloud or cover the filled side of the fabric resulting in a material having aweaker color on the filled side as compared to the unfilled side. Attempts .have been made to overcome this difliculty bynadding a dye to the melting-point (Hercules drop method) within the range of about C. and about 120 C. and more preferably within the range of about 40 C. to about 60 C. By the term dispersion is meant an organic solvent solution, an aqueous emulsion, or an aqueous emulsion formed by dispersing an organic solvent solution of the polymerized terpene resin in water. In addition to the polymerized terpene resin, the dispersion used in providing the various advantageous features of this invention may contain any of the usual textile finishing materials such as starches, gums, talc, softeners, etc.

More particularly, in carrying out the method in accordance with this invention, a textile fabric is treated with a dilute dispersion containing as an essential ingredient a polymerized terpene, resin. After treatment of the fabric with the dispersion, the excess dispersion is removed from the textile fabric and the fabric treated in any suitable manner.

The improved fabric composition and method of application in accordance with this invention are illustrated by the following specific examples, all parts and percentages being by weight unless otherwise specified.

appearance, and the boardiness characteristic of the fabric as contrasted to the smooth, fullbodied and flexible textile desired.-

the prior art binding agents when used alone are eliminated by treating a textile fabric with a dispersion comprising'as an essential constit- EXAMPLE 1 Textile finishing composition containing polymerized terpene resin as the sole binding agent The polymerized terpene resin used in this example has the following properties:

Melting point About -60 0. Color About 30 amber -Odor Balsamlike Appearance Semi-hard resin Step 1' (Formulation of emulsified compositions).-'-'An emulsion of the above-prepared resin was made; using the following'ingredients:

ture was then passed through a suitable homogenizer to produce the desired emulsion.-

Step 2 (Fabric impregnation tratmentsL-A sample of sheeting (2.58 yards) was treated with the above emulsion formed in Step 1, which uent a polymerized terpene' resin, having a 6 emulsion had been diluted to 3% solids by diluting 3 parts of the 33%% solids emulsion with parts of water. The sheeting was impregnated in this dilute emulsion, squeezed, and dried overheated cans at about 250 F. The sheetin was characterized by an increased stillness ,and o fullness as compared to its untreated condition and further characterized by a stiffness factor which increased to 64.4 mg. (Gurley method) as compared to its untreated condition having a stiifening factor of 28 mg. v

1 Examru: 2 Textile finishing composition eontaining polymerized resin (Piccolyte 8-40) as the sole bindpassed through a suitable homogenizer to produce the desired emulsion.

Step 2-(Fabric impregnation treatment) sample of sheeting (2.58 yards) was treated with the above emulsion formed in Step 1, which emulsion had. been diluted to 3% solids by diluting 3 P s Of he /a% solids emulsion with 30% parts of water. The sheeting was impregnated in this dilute emulsion, squeezed, and dried over heated cans at about 250'F. The sheeting was Step 1 (Formulation of emulsified composition) .An emulsion of the above-prepared resin 25 was made using the following ingredients:

' -Parts Piccolyte 8-40 (80% in xylene) 100 Water I -1392 Duponol ME (dry) 0 .8

The emulsion was made by dissolving the 1311-, ponol ME in water The 80% xylene solution was added to the Duponol-water solution with a suitable homogenize'r to produce the desired I emulsion. Step 2 (Fabric impregnation treatment) .A

' sample of sheeting (2.58 yards) was treated with the above emulsion which-had been'dilutedto 40 3% solids by diluting 3 parts of the 33%% solids emulsion with 30% parts of water. The sheeting was impregnated in this dilute emulsion, squeezed, and dried over heated cans at about increased stiffness and fullness ascompared to its untreated condition and further characterized by a stiffness factor which increased to 44 mg. (Gurley method) as compared to its untreated condition having a stifl'ness factor of 28 mg.

- a 8-55 and has the following properties:

Melting point 4 -58 0. Color WW Acid number .1 Less than 4 Appearance. Semi-hard Step 1 (Formation of emulsified composition) .An emulsion of the above-prepared resin was made using the iollowing ingredients:

Y Parts Piccolyte 8-55 (80% in xylene) 100.0 Water .l I 139.2 DuponolME (dry)- 0 '.8

[The emulsion as 'made; by dissolving the nuponol-ME in the water. The xylene solution of resin wasadded to the Duponol-water a 250 F. .The sheeting was characterized by an 45 characterized by an increased stiiiness and fullness as compared to its untreated-condition and further characterized 'by an increase in stiil'ness facton (Gurley method) from 28 mg. (untreated fabric) to 64.4 mg.

EXAMPLE 4 Textile finishing composition containing st ma modified by a polymerized terpene resin (Formulation of composition) .In\this example the polymerized terpene resin having the properties indicated in Example 1 was 'used in combination with cornstarch and tapioca flour mixed in the following proportions:-

Parts Cornstarch 16 Tapioca flour 1 16 Talc Q. 50 Sulfate'd tallow -Q 8 Polymerized terpene resin em-ulsion 37 /2 Water 320 The above mixture was made by cooking together i g mixture was then p 1 through 5 the starch, talc, flour, softener, andwater with constant stirring. .The resin emulsion was added after the starch mixture had reached the boiling point. Boiling was continued for 10 minutes after the resin emulsion'was added.

Test '1 (Fabric impregnation treatment) .A sample of print cloth (80'' by 80") was backfilled with the above resin-starch mixture; squeez ed, and dried over heated cans. The cloth back-filled with this starch-resin formulation was fuller and more firmthan a sample print cloth treated in the same manner with a straight starch mixture made in accordance with the following formulation: 4 v

Parts Cornstar 20 Tapioca flour 20 Talc V 5o Sulfated MOW-a 15 Water 320 The talc dusted out of the print cloth back-filled with the straight starch mixture very badly, especially "when the printscloth was ruilied or torn. However, when the print cloth backfilled torn, very little dusting out was noticed. I

Test 2 (Bye shade test) .In order to illustrate the improvement in the dyed shade in the.l:' ackfilled side of a dyed fabric, the resin-starch composition and the starch composition prepared in accordance with Test 1 were'each back-filled on separate samples of the blue-dyed Indianhead broad cloth and dried, The'appearance of the I back-filled side of the blue fabric finished with any appreciable extent the starch composition was quite cloudy and about 15% weaker-than the unfinished side, whilethe sample finished with the resin-starch composition showed very little eifect of cloudiness and.

solution with stirring. The w s w en 7 comparedtothe unfllled'side.

h the resin mixture was shaken and aaoonaa Textile finishing composition containing starch modified by a polymerized terpene resin (Formulation of composition).-In this 7 example the polymerized terpene resin havingthe properties indicated in Example 2 wa used in combination with cornstarch and tapiocaflour mixedinthe following proportions:

. Parts Cornstarch. l6 Tapioca flour 16 Talc 50 Sulfated tallow 8 Piccolyte 8-40 37 Water 320 The above mixture was made by cooking together the starch, talc, flour, softener, and water with constant stirring. The resin emulsion was added after the starch mixture had reached the boiling point. Boiling was continued for 10 minutes after the resin emulsion was added. Y 1

- Test 1 (Fabric impregnation treatment) -a sample of print cloth (80" by 80") was bMkfilled with the abov resin-starch mixture, squeezed, and dried ove heated cans. The cloth back-filled with this starch-resin formulation was fuller and more firm than 'a'sample print cloth treated in the same manner with a straight starch mixture made in accordance with the' following formulation:

Cornstarch. Tapioca flour 20 Tale Sulfated tal1ow 15 Water "and 320 4/ The talc dusted out of the print cloth back-filled with the starch composition very badly, especially when the print cloth was ruflledpr'tom. However, when the print cloth back-filled with the.

resin-starch mixture was shaken and torn, very little dusting out was noticed.

Test 2 (Due shade test) .--In order toillustra the improvement in the dyed shade in the backfilled side of a dyed fabric the resin-starch composition and the starch composition prepared in accordance with Test 1 were each back-filled on separate samples of blue-dyed Indianhead broad cloth and dried. The appearance of the backfilled side of the blue fabric finished with the starch composition was quite cloudy and about 15% weaker than the unfinished side, while the sample finished with the resin-starch composition showed very little effect of cloudiness and the strength of the color had not been reduced to any appreciable extent on the back-filled side or compared to the unfilled side.

Test 3 (Transparency testxjlo illustrate the transparency of the finish and the strength 01 the film of the resin-starch finishingcomposition, the resin-starch emulsion was cast'in a film on a plate glass and dried: The starch composition made in accordance with Test 1 was cast in a film of thelsamethickness as .the starch-resin film on a glass plate and dried. The film obtained from the starch-resin composition wasconsid'erably more transparent and remarkably more re-' sistant to scratching or dustin'g'out than was the starch film:

p EXAHPLI 6 Textile finishing composition containing starch modified by a polymerized terpene resin (Formulation of comnosition).--In this example, the polymerized terpene resin having the properties indicated in Example 3 was used, in combination with cornstarch and tapioca flour mixed in the following proportions:

Parts Cornstarch 16 Tapioca-flour .16 y Talc 50 Sulfated tallow 8 -Picco1yte-S-55 37% Water 320 The above mixture was made by cooking together the starch, talc, iiour, softener, and water with constant stirring.:,' The resin emulsion wasadded after the starch mixture had reached the boiling point. Boiling was continued for 10 minutes after the resin emulsion was added.

' Test '1 (Fabric impregnation treatmentL -A sample of "print cloth by 80") was backfilled with the above resin-starch mixture, squeezed, and dried-overheated cans. The cloth back-filled with this resin-starch formulation was fuller and more iirm' than a sample print cloth treated in the s mqmanner with a straight starch mixture made in accordance with'the following formulation Parts Cornstarch -4 20 Tapioca flour"; 20 Talc 50 Bulfated tallow.. 15 Water 320 accordance with Test 1 were each back-filled on I separate samples of blue-dyed Indianhead broad cloth and dried. The appearance of the backfilled .side of the blue fabric finished with the starch composition was quite cloudy and about 15% weaker than the unfinished side, whilethe sample finished with. the resin-starch composition showed very little effect of cloudiness and the strength of the color had not been reduced to any appreciable extent on the back-filled side or compared to the unfilled side.

Test-3 (Transparency test) .-"'ro illustrate the transparency of the finish and the strength of the film oi the resin-starch finishing composition, the resin-starch emulsion was cast in a film on a plate glass and-dried. ,The starch composition made in accordance with Test 1 was cast in a film of the same thickness as the starch-resin film on a glass plate; and dried The film .ob-

equipment consisting of dry which has tained from the starch-resin composition was considerably more transparent and remarkably more resistant to scratching or dusting than was the starch film;

In greater detail, the highly desirable features of this invention as herein set forth and compared are realized by treating ina suitable manner the textile fabric as, for example, the sheeting and print cloth of the examples with a dilute dispersion' containing as an essential ingredient a polymerized resin having a melting point within the range of about 30 C. to about 120 C. and preferably within the range of about 40 C. to about60 0., removing excess dispersion from the textile fabric, evaporating the volatile ingradients from the treated textile fabric, and drying in any suitable manner, such as on hot rolls, in a blast of'heated air, with a hot iron at a temperature within the range of about 160 F. to

' composition remaining inthe fabric will, at the end of the procedure, be insufilcient fully to impregnate the individual threads or to form a continuous coating over the surfaces ofthe textile fabric.

exhibit increased color brightness. A hosiery fabric treated in accordance with the invention will have improved run-proof properties.

In making an emulsion of these polymerizedterpene resins, it is preferable to first make a solvent solution of the resins using any of the well-known solvents, such as, for example, xylene, benzene, or naphthalene. It has been found that an 80% solution of the polymerized terpene resin in a solvent as, for example, xylene, I

is satisfactory for the purpose of this invention.

In the preparation of the emulsion for use in the method of this invention, any of the wellknown emulsifying agents may be employed, such as, for example, sodium olea'te, triethanolamine stearate,' Duponol ME (sodium lauryl sulfonate), Nekal 3A" (sodium alkyl naphthalene), as well as other emulsifiers or combinations of emulsifiers. It is desirable in some instances to stabilize the emulsions by passage through a colloid mill or homogenizer. Stabilizin'g agents may be included in the emulsions as desired as, for example, sulfated castor. oil, methyl cellulose, gelatin, gum arable, etc.

In preparing the compositions containin starch modified by a p lymerized terpene resin,

as exemplified in Examples 4, 5, and 6, the starch,

talc, and softener mixture is preferably mixed thoroughly with agitation provided by mechanical means or by steam and heated to boiling. When the mix reaches the boiling point,

The temperature at which the finishing compositionsare applied to' textile fabrics in accordance with this invention is not critical. The usual procedures used in the industry are entirely satisfactory and the use of the usual drying cans and tenter frames is satisfactory. 1 r

The improved product produced in accordance with this invention comprises a textile fabric lieen treated with a dispersion contaming as an essentlal'constituent a polymerized terpene resin. The finished textile fabric is characterized broadly as having an improved, flexible finish. Depending on the type of fabric treated and the auxiliary, finishing agents such as starches, gums, talc, softeners, etc., used with the polymerized terpene resin, the finished textile fabric will-have various-other advantageous properties. Thus, a spun rayon treated with a dispension of thepolymerized terpene resin alone will possess a very satisfactory handle and body. The back-filled fabric produced with use of -starc h, talc, softeners, etc., as auxiliary agents with the polymerized terpene resin in the finishing composition will not besubiect to dusting and brighter both on the'back and the face than. obtainable without the inclusion'of the specific v polymerized terpene resin m thesflnishing compositions. It the fabric has been dyed after the ilnishingtreatfnent, a greater-depth and brightto brealdng of the fabric. Ifthe backnsssbf shade'is obtainable than with comparable finished fabrics iotcontaining the polymerized terpene resin. If the textile fabric has been the emulsion of the polymerized terpene resin is added and the mixture boiled until the starch gelatinizes. On gelatination of the starch, the polymerized terpene resin becomes an intimate part of the starch gel structure, forming a smooth, creamy mixture. The cooking time of the starch mixture is preferably reduced with use of the polymerized terpene resin emulsion, about one-half the normal time usually satisfactory,

The polymerized terpene resin may be used in various proportions in the finishing compositions depending on the weight of fabric desired, the temperature of application, and the particular fabric being treated. The amount of polymerized terpene resin used with the other finishing agents,such as starches, talc, gums, softeners, etc., will depend entirely on the particular effect desired. I

The polymerized terpenes as, for example, the terpene polymers and copolymers which may be utilized in accomplishing the improvements of the textile fabrics described .herein are resins 7 characterized by permanent thermoplasticity and high flexibility. They are essentially water-insoluble and, therefore, remain to a. substantial the polymerization operation in such a manner as to provide a, polymer having a melting point ghlakil'lacteristic within the range hereinbefore set a o 'Terpene polymers and copolymers may be pre pared by procedures well knownin the art. The

are developed. In the back-filling of lining cloth polymerized terpene resin used in Example 1 may be prepared as follows:

To 188 g. of anhydrous aluminum chloride, add 1250 g. of ethylene dichloride, 0001 the mixture to 34 F. and add 750 g. of alpha-pinene during 2% hours with vigorous agitation, maintaining the temperature at about 65 the coolin and agitate-the tion for hour at 60 to 70 F. Cool the solution to 40 F. and add 100 g. of ice with stirring during about minutes, during which time :the temperature will increase to about 120 F. Add to this mixture about 500 cc. of water with agitation for minutes, thoroughly wash the ethyl? ene dichloride solution and remove the ethylene dichloride by steam distillation. The yield will be about 650 g. of resin. The product is then homogeneous soluto 70 F., remove heated to about 260 F. for about hour under a blanket of carbon dioxide as a means of bleaching the color. The physical characteristics of this resin will be as follows:

Melting point 50-60 C. Color About 30 amber Odor Balsam like Appearance Semi-hard resin The polymerization operation of the terpenes may be carried out by means of catalysts other than aluminum chloride, as, for example, fullers earth, activated clay, boron tr-ifluoride, sulfuric acid, phosphoric acid, zinc chloride, diazodinitrophenol borate, complexes of aluminum chloride with inorganic salts such as AlCla-NaCl, phosphoric acid, tetraphosphoric acid, stannous chloride, fiuoboric acid, etc.

Terpene copolymers of acyclic, monocyclic and bicyclic terpenes with other unsaturates such as styrene, coumarone, indene, cyclopentadiene, butadiene, isoprene, and isobutene are also found suitable for the purposes of this invention. C0- polymers of terpenes with halogenated unsaturates as, for example, vinyl chloride, are found operable.-

Hydrogenated products of each of these terpene polymers and copolymers are found desirable for the purposes of this invention.

In accordance with this invention, it is found.

that such polymerized terpene resins possess Very unique properties highly advantageous in textile finishing compositions. plastic type and'having resinous properties, such polymerized resins provide adhesive qualities to other binding agents such as starches, and modifies these binding agents in such a way that the materials no longer retain their undesirable characteristics of the polymerized resin to produce the smooth, full-bodied and flexible textile desired.

. The invention is applicable to either pure or back-filled finishes. Thus, in the finishing of spun rayon, a very satisfactory handle and body merized terpene resin usual starch treatment. In addition,

with the usual starches, talc and softeners, this improved method and finishing composition provide a finished fabric which is free from dusting out 01 starch and talc and which has improved flexibility and resistance to breaking of the fabric. In the finishing of colored fabrics with starch, this improved finishing composition and method provide a finish which possesses increased color brightness over that obtainable with the the starch Particles are more firmly adherent to the fabric. A similar increased color brightness may be obtained by dyeing the fabric after it has been finished according to this invention. In the finishing of hosiery, this improved method binds the cross threads at their point of contact and thereby produces runproof properties.

The many advantage of the treatment of textile fabrics with finishing compositions containing as an essential ingredient a polymerized terpene resin have been described in the above with particular reference to the type of fabric treated and to the effect of the specific polymerized terpene resin on the usual finishing materialssuch as starches, gums, talc, softeners, etc., when used in conjunction with such materials. In addition to these advantages, it will be readily apparent that the finishes are easy to apply. A greater general uniformity of finishes is obtainable and at a cost which presents a reduction in finishing cost. This advantage results from the fact that greater yardage is obtained, for example, from a starch composition containing the specific polythan is possible without it, the viscosity being lower. The greater uni-' formity of finish is a result of a more even spread and better penetration of the solids into the fabric because of better dispersion of the particles of fine dimensions. Due to the resinous character term textile fabric Being of the thermo- 'of the polymerized terpene resin used,-the treated textile fabric has a greater tensile strength than obtained with straight starch finishes.

Where, in the specification and claims, the has been used, the term intended to cover yarns as well as knitted or woven fabrics.

What I claim and desire to protect by Letters Patent is:

1. A textile fabric fiinishing composition comprising as a binding agent starch modified with a polymerized terpene hydrocarbon resin.

Y 2. A textile fabric finishing composition comprising as a binding agent cornstarch modified with a polymerized terpene hydrocarbon resin.

3. A textile fabric containing starch modified 

